In der Arbeit werden Aufschluss- und Sortierergebnisse miteinander kombiniert, um die Anreicherung des Wertstoffs unter Berücksichtigung beider Teilprozesse auf einer vergleichbaren Basis bewerten zu können. Hierfür werden der Literatur vorhandene Modelle entnommen und erweitert, wodurch sich neuartige Parameter definieren lassen. Am Beispielsortierschritt Magnetscheidung wird anhand zweier unterschiedlicher Erze die Beurteilung der Teilprozesse auf Grundlage des vorgeschlagenen Vorgehens dargestellt. Mit Hilfe der Untersuchung der magnetischen Eigenschaften der Erze kann der Einfluss des gewählten Merkmals auf den Verlauf der berechneten Grenzkurven gezeigt werden. Weiterhin erfolgt eine Darstellung der Möglichkeiten durch die Nutzung moderner mineralogischer Analysemethoden zur Berechnung von Mineralsuszeptibilitäten, basierend auf Aufschluss- und Suszeptibilitätsmessungen von Merkmalklassen, sowie das direkte Berechnen von Trennfunktionen mit Hilfe von Aufschlussanalysen der Trennprodukte.

This thesis focuses on fundamental aspects of microfluidic systems and applies relevant findings to innovative designs for advanced particle manipulation applications. Computational Fluid Dynamics (CFD) is adopted for fluid modeling, based on the Finite Volume method. The accuracy of the solutions obtained is confirmed by grid sensitivity analysis and by comparisons with experimental work. Curved microchannel features and the induced Dean flow are studied through a parametric space exploration and simulations. The Lagrange-Euler coupling method – Surface Marker Point methodology – is applied to simulate large-size particles (of comparable size to the channel). Through this simulation approach, all the forces on such particles are directly derived through solving the governing equations and the influence of these particles on the flow is considered in a fully coupled manner. A new approach – the Frozen Flow & Flow Correction Coefficient method – is developed, making trans-relaxation-time simulations possible and improving computational efficiency significantly, for 3D simulations of arbitrary shape and size microparticles in complicated microfluidic channels. Detailed comparisons between simulation results and experiments involving particle sedimentation and particle equilibrium position have been conducted for methodology validation. Mechanisms of hydrodynamic particle manipulation are then studied, including hydrodynamic focusing and separation. It is found that the Tubular Pinch effect, Dean flow and the Radial Pressure Gradient effect interact to yield two distinct particle separation mechanisms. For advanced applications, particle focusing, non-magnetic and magnetic separation for neutrally buoyant particles are proposed, based on newly gained insight on the above-mentioned mechanisms. Appropriate channel designs have been proposed both for particle focusing and size-based particle separation, while the vertical-magnetic-Dean separation scheme is highlighted for magnetic separation. Finally, a new integrated system is proposed, that combines the above novel designs into a device-like ensemble. It promises to offer functionality for biomaterial separation and detection, including different types of cells, antigens and biomarkers.

Nucleic acid technology has assumed an essential role invarious areas ofin vitrodiagnostics ranging from infectious diseasediagnosis to human genetics. An important requirement of suchmolecular methods is that they achieve high sensitivity andspecificity with a fast turnaround time in a cost-effectivemanner. To this end, in this thesis we have focused on thedevelopment of sensitive nucleic acid strategies thatfacilitate automation and high-throughput analysis. The success of nucleic acid diagnostics in the clinicalsetting depends heavily on the method used for purification ofthe nucleic acid target from biological samples. Here we havefocused on developing strategies for hybridisation capture ofsuch templates. Using biosensor technology we observed that thehybridisation efficiency could be improved using contiguousoligonucleotide probes which acted co-operatively. Byimmobilising one of the probes and annealing the second probein solution, we achieved a marked increase in target capturedue to a base stacking effect between nicked oligonucleotidesand/or due to the opening up of secondary structure. Suchco-operatively interacting modular probes were then combinedwith bio-magnetic bead technology to develop a capture systemfor the extraction of hepatitis C RNA from serum. Viral capturewith such co-operatively interacting probes extracted 2-foldmore target as capture with only a single probe achieving asimilar sensitivity to the conventional extraction protocol. Ananalogous strategy was designed to enrich for sequencingproducts prior to gel electrophoresis removing sequencingreagents and template DNA which interfere with the separationand detection of sequencing ladders, especially in the case ofcapillary gel electrophoresis. This protocol facilitates highthroughput clean-up of cycle sequencing reactions resulting inaccurate sequence data at a low cost, which is a pre-requisitefor large-scale genome sequencing products. Currently, a large effort is directed towards differentialsequencing to identify mutations or polymorphisms both in theclinical laboratory and in medical genetics. Inexpensive, highthroughput methods are therefore required to rapidly screen atarget nucleic acid for sequence based changes. In the clinicalsetting, sequence analysis of human immunodeficiency virus(HIV-1) is used to determine the presence of drug resistancemutations. Here we describe a bioluminometric pyrosequencingapproach to rapidly screen for the presence of drug resistancemutations in the protease gene of HIV-1. This sequencingstrategy can analyse the protease gene of HIV-1 from eightpatients in less than an hour and such non-gel based approachesshould be useful in the future in a clinical setting for rapid,robust mutation detection. Microarray technology facilitates large-scalemutation/polymorphism detection and here we developed amicroarray based single nucleotide polymorphism (SNP)genotyping strategy based on apyrase mediated allele specificextension (AMASE). AMASE exploits the fact that mismatchedprimers exhibit slower reaction kinetics than perfectly matchedprimers by including a nucleotide degrading enzyme (apyrase)which results in degradation of the nucleotides before themismatched primer can be extended. We have successfully typed200 genotypes (14% were incorrect without apyrase) by AMASEwhich cluster into three distinct groups representing the threepossible genotypes. In the future, AMASE on DNA microarraysshould facilitate association studies where an accuracy&gt;99%is required. <b>Keywords:</b>nucleic acid capture, modular probes,biosensor, bio-magnetic separation, hepatitis C, sequencing,pyrosequencing, mutation detection, HIV-1, drug resistance,SNP, allele-specific extension, apyrase, genotyping.

<p>Nucleic acid technology has assumed an essential role invarious areas of<i>in vitro</i>diagnostics ranging from infectious diseasediagnosis to human genetics. An important requirement of suchmolecular methods is that they achieve high sensitivity andspecificity with a fast turnaround time in a cost-effectivemanner. To this end, in this thesis we have focused on thedevelopment of sensitive nucleic acid strategies thatfacilitate automation and high-throughput analysis.</p><p>The success of nucleic acid diagnostics in the clinicalsetting depends heavily on the method used for purification ofthe nucleic acid target from biological samples. Here we havefocused on developing strategies for hybridisation capture ofsuch templates. Using biosensor technology we observed that thehybridisation efficiency could be improved using contiguousoligonucleotide probes which acted co-operatively. Byimmobilising one of the probes and annealing the second probein solution, we achieved a marked increase in target capturedue to a base stacking effect between nicked oligonucleotidesand/or due to the opening up of secondary structure. Suchco-operatively interacting modular probes were then combinedwith bio-magnetic bead technology to develop a capture systemfor the extraction of hepatitis C RNA from serum. Viral capturewith such co-operatively interacting probes extracted 2-foldmore target as capture with only a single probe achieving asimilar sensitivity to the conventional extraction protocol. Ananalogous strategy was designed to enrich for sequencingproducts prior to gel electrophoresis removing sequencingreagents and template DNA which interfere with the separationand detection of sequencing ladders, especially in the case ofcapillary gel electrophoresis. This protocol facilitates highthroughput clean-up of cycle sequencing reactions resulting inaccurate sequence data at a low cost, which is a pre-requisitefor large-scale genome sequencing products.</p><p>Currently, a large effort is directed towards differentialsequencing to identify mutations or polymorphisms both in theclinical laboratory and in medical genetics. Inexpensive, highthroughput methods are therefore required to rapidly screen atarget nucleic acid for sequence based changes. In the clinicalsetting, sequence analysis of human immunodeficiency virus(HIV-1) is used to determine the presence of drug resistancemutations. Here we describe a bioluminometric pyrosequencingapproach to rapidly screen for the presence of drug resistancemutations in the protease gene of HIV-1. This sequencingstrategy can analyse the protease gene of HIV-1 from eightpatients in less than an hour and such non-gel based approachesshould be useful in the future in a clinical setting for rapid,robust mutation detection.</p><p>Microarray technology facilitates large-scalemutation/polymorphism detection and here we developed amicroarray based single nucleotide polymorphism (SNP)genotyping strategy based on apyrase mediated allele specificextension (AMASE). AMASE exploits the fact that mismatchedprimers exhibit slower reaction kinetics than perfectly matchedprimers by including a nucleotide degrading enzyme (apyrase)which results in degradation of the nucleotides before themismatched primer can be extended. We have successfully typed200 genotypes (14% were incorrect without apyrase) by AMASEwhich cluster into three distinct groups representing the threepossible genotypes. In the future, AMASE on DNA microarraysshould facilitate association studies where an accuracy>99%is required.</p><p><b>Keywords:</b>nucleic acid capture, modular probes,biosensor, bio-magnetic separation, hepatitis C, sequencing,pyrosequencing, mutation detection, HIV-1, drug resistance,SNP, allele-specific extension, apyrase, genotyping.</p>

M.Tech. Engineering: Chemical. / Aims at demonstrating the application of semi-continuous and continuous magnetic adsorption separation (MAS) techniques to extract Cr (VI) ions from wastewater streams using PPy-Fe3O4 nanocomposite. Specifically, the research aims to achieve the following objectives: to design, synthesize and characterize new generation PPy-Fe3O4 nanocomposite with varied magnetite composition for hexavalent chromium removal ; to generate batch adsorption kinetic data in a continuously stirred tank reactor (CSTR) and apply existing kinetic models to aid in water treatment system design.; to design and construct magnetic adsorption separation (MAS) device that can operate in a semi-continuous and continuous mode and explore their performances and to optimize the systems' performance.

The continuous flow separation of magnetic particles from a mixture of particles could improve the performance of magnetic bead based assays but the formation of agglomerates limit the separation efficiency. Bead agglomerates are formed as a result of magnetic binding forces while the hydrodynamic fluid environment strongly influences their movement. The ability to predict the interaction between nearby beads will help to determine a threshold separation distance which will be recommended for use when obtaining measurement within a magnetic bead assay for a specified time interval. The introductory part of this thesis explored the development of a two dimensional numerical model in Matlab which predicts the trajectory pattern as well as magnetic induced velocities between a pair of super-paramagnetic beads suspended in water within a uniform field. The movement of a bead pair interacting due to both magnetic and hydrodynamic forces within a magnetophoretic system was recorded using an optical system; the beads' movements were compared with the simulated trajectories and gave a good agreement. The model was used to predict the shortest agglomeration time for a given separation distance which is of practical benefit to users of bead based assays. The concluding part of this thesis expanded the simulation into a three dimensional model to predict the interactions among three super-paramagnetic beads within a magnetophoretic system. In order to determine the height of the magnetic beads, a Huygens-Fresnel model was implemented in Matlab which was compared with off-focused diffracted images of the beads viewed under an optical system. A good comparison was obtained by comparing the simulated three-dimensional trajectories with experimental data.

This dissertation deals with two prospectives of rare earth technology. It’s application in magnetic cooling as well as its harvesting and recycling phase. The emphasis is on mapping and manipulating the transport processes of energy and mass, during magnetic cooling and rare earth magnetic separation, under the influence of magnetic field. Distinguished by the driving force of flow field, they belong to the context of magnetohydrodynamics and ferrohydrodynamics, respectively. Multiple aspects are investigated with respect to magnetic cooling. First, the transient dynamics of heat transfer from two periodically magnetized gadolinium (Gd) plates into a heat transfer fluid (n-decane) is studied. It demonstrates that the propagation of the thermal fronts emanating from the Gd plates after magnetization or demagnetization obeys a √t-dependence. A finite time required for magnetization and demagnetization causes a spatially delayed propagation of the thermal fronts. The diffusive heat flux, derived from the temperature profiles, experiences a drop down by about 80% after first 3 seconds while the percentage of thermal energy transferred into n-decane experiences a maximum there. With a stagnant fluid, this work provides reasons for lower bounds of geometry and operation frequency of a simplified parallel-plate structure in the diffusive limit. Furthermore, the potential of magnetohydrodynamic (MHD) convection to increase heat transfer during magnetic cooling is tested. To do this, a section of an active magnetic regenerator is considered, namely a flat gadolinium plate, immersed in an initially stagnant heat transfer fluid (NaOH) which is placed in a cuboid glass cell. To create the MHD flow, a small electric current is injected by means of two electrodes and interacts with the already present magnetic field. As a result, a Lorentz force is generated, which drives a swirling flow in the present model configuration. By means of particle image velocimetry and Mach-Zehnder interferometry, the flow field and its impact on the heat transfer at the gadolinium plate is analyzed. For the magnetization stage, a heat transfer enhancement by about 40 % can be achieved even with low currents of 3 mA is found. In parallel to enhance the heat transfer by an actively stirring of the heat transfer fluid by means of MHD, alternative fluid candidate is also investigated. A room temperature eutectic liquid metal GaInSn, with superior Pr≈ 0.03, and comparable viscosity like that of water is tested in a segment of parallel plate AMR. Due to the high electric conductivity, velocity field of GaInSn contrasting to that of aqueous based ones is strongly influenced by magnetic field due to Lorentz force. Therefore, preliminary velocity measurements by means of ultrasound doppler velocimetry with a quasi homogeneous static magnetic field (220 mT) in a duct channel at the non-conducting Shercliff walls are conducted. The Hartmann walls are constituted of two parallel Gd plates. The second part of this dissertation, rare earth harvesting and recycling, aims to answer the question of why an enrichment of paramagnetic ions can be observed in a magnetic field gradient despite the presence of a counteracting Brownian motion. For that purpose, a rare-earth chloride (DyCl3) solution is studied in which weak evaporation is adjusted by means of small differences in the vapor pressure. The temporal evolution of the refractive index field of this solution, as a result of heat and mass transfer, is measured by means of a Mach–Zehnder interferometer. A numerical algorithm is developed that splits the refractive index field into two parts, one space-dependent and conservative and the other time-dependent and transient. By using this algorithm in conjunction with a numerical simulation of the temperature and concentration field, it is able to show that 90% of the refractive index in the evaporation-driven boundary layer is caused by an increase in the concentration of Dy(III) ions. A simplified analysis of the gravitational and magnetic forces, entering the Rayleigh number, leads to a diagram of the system’s instability. Accordingly, the enrichment layer of elevated Dy(III) concentration is placed in a spatial zone dominated by a field gradient force. This leads to the unconditional stability of this layer in the present configuration. The underlying mechanism is the levitation and reshaping of the evaporation-driven boundary layer by the magnetic field gradient.

Treatment of wastewater using magnetic technology is a rising field. In this thesis, the latest research on the subject is reviewed and several adsorbents with different coatings, which impart them unique properties, are discussed. Separation of particles from aqueous solution using magnetic technology is more convenient compared to conventional techniques, such as filtration and centrifugation. The adsorbents described in this thesis are effective for adsorption of several types of contaminants, such as heavy metals and different types of dyes.    Magnetic microspheres were synthesised using porous polystyrene microspheres as template. The microspheres were first sulfonated using chlorosulfonic acid followed by stirring in the presence of ferrous chloride which then was oxidised and magnetic nanoparticles were formed on the surface.    The sulfonated microspheres had a surface area of 420 m2/g and the magnetic 175 m2/g, indicative of Fe3O4 nanoparticles were successfully formed in the pores. The weight fraction of the Fe3O4 nanoparticles in the magnetic microspheres was 33 %.    Adsorption and desorption studies of the cationic dye, methylene blue, using mesoporous magnetic microspheres were performed. The results show that the mesoporous magnetic microspheres have good ability to adsorb methylene blue at low concentrations. In a cycle study the adsorption efficiency were nearly 100 % throughout the study. Using a 6/4 EtOH/H2O with saturated KCl solution the desorption efficiency in the cycle study were about 95 %.      The microspheres were used as carriers for TiO2 in order to overcome the problem with the separation of TiO2 from solution. The TGA results show that the microspheres contained about 12 % of TiO2. The TiO2 coated microspheres were used for the photocatalytic degradation of phenol. However, the TiO2 microspheres did not work. This was a result from that the phenol had too little contact with the TiO2. A possible way of solving this problem could be to decrease the size of the microspheres, thus increase the surface area.    Lysozyme was adsorbed and separated using the porous microspheres. The lysozyme adsorption worked best at pH 9.6, which is the pI for lysozyme. The lysozyme could be extracted from the microspheres by using a pH 13 buffer. Also, by using MeOH/H2O and EtOH/H2O solutions with saturated KCl the lysozyme could be desorbed. An adsorption and desorption mechanism was also presented. / Vattenrening med magnetisk teknologi är en ny och alltmer uppmärksammad teknik. Magnetisk separation är ett enkelt och snabbt sätt att separera något från en lösning. Magnetisk separation är mer lätthanterligt jämfört med traditionell separationsteknik såsom centrifugering och filtrering.  Med porösa polystyren mikrosfärer som mall, syntetiserades magnetiska mikrosfärer. Först så sulfonerades mikrosfärerna med klorosulfonisk syra, följt av att de rördes om i en järnkloridlösning. Magnetiska nanopartiklar bildades i porerna och på ytan av mikrosfärerna.    Sulfonerade mikrosfärerna hade en specifik ytarea på 420 m2/g och de magnetiska 175　m2/g, detta indikerar att Fe3O4-nanopartiklar bildades på ytan och i porerna. Massfraktionen av Fe3O4 var 33 %.    Adsorption- och desorptionsstudier på de magnetiska mikrosfärerna utfördes. Färgämnet metylblått användes i studien. Resultaten visade att magnetiska mikrosfärerna hade en bra adsorptionsförmåga vid låga koncentrationer av metylblått. Cykelstudier visade att adsorptionsverkningsgraden var nära 100 % under flera adsorptionscykler. Desorptionsförsök med olika lösningsmedel visade att en mättad KCl 6/4 EtOH/H2O lösning gav en desorptions-verkningsgrad på ca 95 %.   Mikrosfärerna användes som mall och kärna för att syntetisera en TiO2-fotokatalysator, detta för att överkomma problemet som finns med separation av rent TiO2 pulver från lösning. TGA resultaten visade att mikrosfärerna innehöll ca 12 % TiO2. De syntetiserade TiO2-mikrosfärerna användes till att bryta ner fenol fotokatalytiskt. Dock fungerade inte detta experiment. En anledning var att fenolen hade för lite kontakt med TiO2. En lösning på detta problem är att använda mikrosfärer med högre specifik ytarea.    Proteinet lysozym användes som modellprotein för försök att separera proteiner från lösning genom att använda porösa mikrosfärer. Resultatet visade att lysozym kunde adsorberas vid pH 9.6. Med en pH 13 buffer kunde lysozymet sedan extraheras från mikrosfärerna. En mekanism för adsorptionen och desorptionen på mikrosfärerna presenterades.

Tungsten (W) is listed among the European Union (EU) critical raw materials (CRMs) for its supply risk and economic importance. Primarily, tungsten is produced from scheelite and wolframite mineral ores with 0.08-1.5% tungsten trioxide (WO3) grade. However, as primary deposits for these resources are becoming less or lower in grade, alternative sources need to be explored. These alternative tungsten sources include scrap from end-of-life products, mine waste and rejects from the ore beneficiation processes (tailings). The latter alternative source is the focus within this thesis. Historical tailings repositories often pose environmental risks but may also become secondary sources of CRMs. This is because of relatively high minerals and metals content due to less efficient extraction methods and/or relatively low metal prices at the time of active mining. Therefore, reprocessing of such tailings is not only a supply risk-reducing measure but also an approach to remediation that contributes to the mining industry’s aim of moving towards a circular economy. The aim of this thesis has been to develop efficient methods for separating valuable minerals from the tailings in order to leave behind a stable and environmentally safe residue. Geometallurgical studies were conducted by collecting drill core samples from the Smaltjärnen tailings repository in Yxsjöberg, Sweden, for evaluating the potential of this repository for further processing. The tailings were originally produced from the ore that was mined by Yxsjö Mines while it was in operation from 1935 to 1963, with average ore grades of 0.3-0.4 wt.% WO3, 0.2 wt.% Cu and 5-6 wt.% fluorspar. The exploited minerals were scheelite for W, chalcopyrite for Cu and fluorspar. The tailings repository is estimated to have about 2.2 million tons of tailings covering an area of 26 hectares, with elemental concentrations of 1-2 wt.% S, 0.02-0.2 wt.% Cu, 0.02-0.3 wt.% W, 0.02-0.04 wt.% Sn and 0.02-0.03 wt.% Be. Sampling and characterization of the historical tailings were conducted based on geometallurgical units (i.e. a distinction between different layers and locations in the repository), followed by metallurgical test work. The tailings were characterized with regard to color and granulometry, particle size distribution, chemical composition, scheelite mineral occurrence, texture and mineral liberation, as well as mineralogical composition. Based on a comprehensive literature survey, tailings characteristics, and assessment of the earlier processes from which the Yxsjöberg tailings were produced, feasible separation methods were pre-selected involving dry low-intensity magnetic separation (LIMS) and high intensity magnetic separation (HIMS), enhanced gravity separation (EGS) using a Knelson concentrator, and batch froth flotation. The average WO3 and Cu concentration in these tailings based on the sampled locations was 0.15 % and 0.11 % respectively. Applying them to the estimated 2.2 million tons of tailings in this repository gives approximately 3300 tons of WO3 and 2512 tons of Cu. From the metallurgical test work, several feasible processing routes have been identified that need to be further assessed based on the economic and environmental criteria. / REMinE (Improve Resource Efficiency and Minimize Environmental Footprint)

The theoretical part of this doctoral thesis provides a comprehensive overview on the topic of preparation and subsequent utilization of magnetic derivatives of biological materials for xenobiotic separation from water. Main attention is paid to magnetic modification of waste materials and by-products originating from agricultural and food industry, which represent widely available and low-cost materials, and also to magnetic modification of microbial cells. In addition to the description of magnetic particle preparation and individual developed techniques of magnetic modification, a brief characterization of selected pollutants and a detailed table overview on utilization of magnetically responsive biomaterials for biosorption of organic dyes, heavy metals, pharmaceutical and personal care products together with ubiquitous industrial endocrine disruptors and also of crude oil derivatives is presented. Experimental part of this thesis is focused on the preparation and optimization of new types of magnetic materials. Emphasis is placed on the employment of simple, fast and simultaneously low-cost magnetic modification techniques (e.g., postmagnetization using microwave-synthesized magnetic iron oxides or one-step modification by magnetic fluids). Selected plant materials (barley and rye straw) were chemically modified to significantly (up to five-times) increase the maximum adsorption capacities for tested dyes. All prepared biomaterials exhibited a great magnetic response and simultaneously relatively high adsorption capacity for selected xenobiotics under experimental conditions used. Factors substantially affecting adsorption process, such as pH, initial concentration, incubation time or temperature were also studied. Adsorption equilibrium data were assessed using Langmuir, Freundlich or Sips isotherm models. Experimental data from time dependence study were analyzed by chosen kinetic models, namely the pseudo-first-order and pseudo-second-order ones and by intraparticle diffusion model. Thermodynamic parameters (Gibbs free energy, enthalpy and entropy) describing the nature of adsorption were also included in study.